Use of a blend of tertiary alkyl mercaptans in emulsion polymerization



, IN EMULSION POLYMERIZATION Original Filed Feb. 2, 1945 Apr1l24, 1951 w. cRoucH ET AL USE oF A BLEND oF TERTIARY ALKYL MERCAPTANS 2 Sheets-Sheet 1 AllSoDSlA DISNIULN\ www MIN

April 24, 1951 w, w. cRoucH ET AL 2,549,962

USE oF A BLEND of" TERTIARY ALKYL MERCAPTANS IN EMuLsIoN POLYMERIZATION original Filed Feb. 2, 1945 2 Smets-She 2 INVENTORS ww. @ROUGH BY 5G, MARHOFER MWL 'l ATTORNEY Patented Apr. 24, 1951 USE OF A BLEND OF TERTIARY ALKYL MERCAPTANS IN MERIZATION EMULSION POLY- Willie W. Crouch, Bartlesville, Okla., and Edwin G. Marhofer, Phillips, Tex., assignors to Phillips Petroleum Company, a corporation of Delaware Original application February 2, 1945, Serial No.

575,819. Divided and this application September 11, 1950, Serial No. 184,278

1 Claim.

This invention relates to the production of high molecular weight polymers. It is particularly applicable to the production of synthetic rubber by the polymerization of polymerizabl'e organic compounds in an aqueous emulsion. In one of its more specific aspects this invention relates to the use of mixtures of certain mercaptans as modifying agents in the emulsion polymerization of butadiene-styrene and other related comonomer systems whereby the quality of the polymerizates is greatly improved. This application is a division of our copending application Serial No. 575,819 led February 2, 1945.

Synthetic rubber is made by polymerization of polymerizable organic compounds under controlled polymerization conditions. The term synthetic rubber is used broadly to include the polyanerizates of oleiins, diolens, styrene and its derivatives, alkyl esters of acrylic and alkacrylic acids (such as methyl methacrylate), and other compounds having at least one active CH2=C= group. These compounds are polymerized alone or in admixture with one another to form products having some of the characteristic properties of synthetic rubber. When a, mixture of two or more of these compounds is subjected to polymerization conditions, a copolymer is formed in which the components form high molecular weight molecules by the linking together of the different individual component monomers. have found that the synthetic product produced by the polymerization of a polymerizable organic compound is improved by the addition of a blend of tertiary aliphatic mercaptans to the monomeric compound to be polymerized prior to the polymerization thereof. This is particularly effective in the polymerization of butadiene in yan aqueous emulsion with suitable comonomers, for example, styrene, derivatives of styrene containing an active CH2=C= group, acrylonitrile, methacrylonitrile, methyl acrylate, methyl methacrylate, etc., to form copolymers. Buna-lS (or GR-S) is an example of the most important synthetic rubber so produced `at the present time.

Itis well known that copolymers of the Buna-S type are unsuited for use as synthetic rubber unless the emulsion polymerization is carried out in the presence of modifying agents. The general function of modiers is to eliminate or substantially reduce the formation between polymer units of cross-linkages leading to the production of geltype products which render the polymerizates tough, hard and generally refractory toward subsequent process operations. Further beneficial effects of modifying agents are frequently manifested in increased polymerization rates. The most effective modifying agents heretofore known to the art have been selected alkyl mercaptans and especially the primary alkyl mercaptans having about 12 carbon atoms per molecule.

It has now been found that tertiary alkyl mercaptans, especially those selected from the group having 8 to 16 carbon atoms per molecule, have a comparable beneficial modifying effect on Buna-rs polymerizates. Unexpectedly, however, 4we have found that blends of two or more selected tertiary mercaptans from the above group exert a modifying action superior in over-all effect to any of the individual mercaptans included in the blends. The polymerizates prepared in the presence of our novel blended modifier compositions are more uniform with respect to molecular weight range and therefore have properties `which are superior to those of polymerizates modified in the conventional manner. Thus when a modiner of uniform carbon content is employed, the rate of depletion of modifier is such than an overmodiiied polymer of inadequate chain length is produced in the early stages of polymerization. Since excessive quantities of modifier have been consumed, cross linking sets in during the final phase of polymerization as is evidenced by a very rapid rise in average molecular weight.- Although both overand under-modification have resulted, the average molecular weight of the final prodf uct is suiciently high to permit processing operations; however, such polymers have poor aging properties. This lack of control over the rate of reaction of modifier results in a product containing a proportion of polymer of objectionably low molecular weight and another portion having excessively high values. With the blended modiiiers of the present invention, the above objections are overcome due to the fact that the mercaptan components are consumed at different rates. The net effect of our blended modifiers is to produce a relatively uniform modification with elimination of cross linking during the later stages of polymerization. Thus, finished polymer of the same average molecular 4weight is much more homogeneous when modified |with a blend of process for the production of high molecularV weight polymers.

Another object is to provide an improved process for polymerization of polymerizable organic compounds in an aqueous emulsion.

tertiary aliphatic mercaptans:

Modifier Parts by wt.

t-octyl mercaptans 0. 20 t-dodccyl mcrcaptansi 0. 28 t-tetradecyl mercaptans 0. 34

The above identified mercaptans are derived from mixtures of isomeric olefins by direct catalytic condensation with hydrogen sulfide. The so-called t-octyl mercaptans, for example, are comprised of many different isomers having 8 4carbon :atoms per molecule. We have found that Y such fractions; of narrow boiling range tend to smi another object is to provide such a proc;

ess -which is particularly useful for the production of polymerizates of theBuna-S type. Y

A further object is to provide such a process in which a blend of two or more tertiary aliphatic mercaptans is used as a modifier for the polymerization.

In one embodiment of the present invention, a

behave as a single mercaptan when used as a polymerization modifier. The same'condition is true of the t'dodecyl and t-tetradecyl mercaptans listed above. In order to specifically define the synthetic tertiaryaliphatic mercaptans of this invention, physical properties of selected molecular weight groups are given in the subjoined tabulation:

t-Mercaptans Cs Cn C14 C15 Sp. gravity at 60 -IEX/60 F 0.856 0.871 0. 877 0. 883 Av. molecular welght. Y 145 193. 3 i 230 249 RSH sulfur, wt. per cent.- p 2l. 6 15.9 1l. 9 10.3 RSH i1punty, Wt, per cent 97+ 96. 8 85. 6 80 YDist ation, F 1 (760 mm.) 2 (5 mm.) 2 (5 mm.) 2 (5 mm.) itlal 301 177 Y 21 252 50% cond 319 V195 237 267 80% cond 324 202 287 90% cond 328 '206 247 305 95% cond 333 212 252 dec.

1 ASTM DSG-40. l

2 Rubber Reserve Company Test Method L. YM..2.5.6.v

conventional polymerization recipe'is employed.

While the preceding representative mercaptan fractions exert avmodifying action comparable with other commercial modifiers, we have now found that polymers'of superior characteristics Y can be realized by utilizing blends of our tertiary Component Parts by wt.

Butadiene V 75 Sty/rene Y Soap 5 Potassium persulfate 0.3 Water- 180 I Mercaptan. Variable.

k',lemperature 50 C.

The quantity of modifier used in any recipe is dependent on the type of mercaptan or mercaptans 'used vand is determined by experiment. For example, tovobtain an acceptable polymerizate for use in synthetic rubber ywith a Mooney viscosity of -55 the conversion is stopped at about 77 per cent of the monomer charge. These conditions are selected to give a gel-free polymeric procedure. An emulsion of the recipe ingredients along with the necessary quantity of modier is agitated for 12 hours at 50 C. The resultant latex is vtreated with phenyl-beta-naphthylamineV antioxidant followed by coagulation. The crude polymer is washed and dried in preparation for evaluation and/orsubsequent process steps. `In this manner, gel-free products meeting the criteria.'A of monomer conversion, Mooney viscosity and processability are obtained With the following mercaptans to give a modifier of variable carbon content. The modifying effect of these blends is such as to result in polymer characteristics entirely different from the'effect that could be predicted from the individual behavior of the blend components. The reason for this synergismY in modifying action is not known, but it is apparently related in some obscure fashion torelative reaction rates. By virtue of this newly discovered method of proper blending of tertiary'mervcaptans,.we are nowable to obtain a smooth rate of modification throughout the entire polymerization period. Under the conditions used heretofore, where a non-uniform rate of modifier depletion occurs, the polymer product represents a combination of over-modified and under-modified components. It is obvousthat a more homogeneous polymer, of the same average molecular weight as obtained with previous unitary modifiers, could be produced'by simply'increasing the polymer size in the early stages of polymerization and eliminating to a large extent the extremelyk high molecularv weight material kordinarily produced in the latter stages of polymerization. In this connection it has been shown by Kemp and Straitiff (Ind. Eng. Chem. 36, 707 (1944)) that the most desirable polymersof the Buna-Stype are those `which do not contain large amounts of material of either very high or very low .molecular weight. That our blended modifiers tend to produce a more uniform product is attested by data to be presented later wherein the ratio of polymer molecular weights at various stages of conversion to that ofthe final product are compared'rwith ventional unitary modifiers.'

similar data derived from experiments using con- 5. In order to demonstrate: the improved results:` attributable to our blends of specified tertiary mercaptans, comparable polymerization experiments were carried out using as modifiers the fractionated samples of Ca, C12, C14 and C16 tertiary mercaptans previously described. The results obtained with the individual unit modifiers were then compared with experiments wherein blends of the mercaptanfractions lwere used for the same purpose. In each test run, the standard. GR-.S recipe was employed along with sufficient added modifier to result in about 77 per cent conversion of monomers to polymer, having a Mooney viscosity of 45-55. In experiments involving nonblended modifier, the proportions of mercaptan are those previously given. The difference in behavior of the various modifiers during the progress of the polymerization was followed by periodic withdrawal of samples to determine extent of conversion and intrinsic viscosity of the product polymer. Since intrinsic viscosity is a measure of molecular weight (cf. Kemp and Peters, Ind. Eng. Chem., 23, 1263 (1941)), the experimental results may be reported in terms of average molecular weights of polymer through the use of a simple mathematical relationship.

TABLE I Variation in molecular weights of GR-S polymers modified with various tertiary mercaptan compositions Average Molecular Weight of Polymer Samples 1 The blend composition consisted of 1 part Cs, 2 parts C12 and 2 parts Ca tert. mercaptans.

In the critical polymerization range lying between 50 and 77 per cent conversion of monomers, the rapid transition from relatively lowl to relatively high molecular weight polymers has been greatly reduced by the use of blended modifiers without reducing the ultimate average molecular weight. The results achieved through the use of our blended modifiers are even more striking when the above data are presented in such a form as to show the actual data obtained with blended mercaptans in comparison with a calculated expected average eifect. Thus, knowing the proportion of each mercaptan in the three component blend, the effect of each component on the molecular weight of GR-S polymer, and assuming that each component exerts its own modifying action 1without synergistic action, a hypothetical set of data similar to that of Table I can be calculated. Such calculated data are presented in Table II along with data obtained using the actual blend. Inspection of the table reveals the unexpected and beneficial synergistic action of the blended tertiary mercaptans.

'I'ABLE` I1 Comparisouof .predictedl and actual modifying action of blended t-rrzercaptaus` :AverageMolelcular Weight oi Poymers Monomer conversion 50% 60% f 70% 77% HypcthoticalMercaptanblendx 123', 000 :161,000 246,000 343,000 Actual Mereaptanblend 1..-.. 152,000 f224,000 328, 000 352,000

TABLE.` 111 Homogeneity of modified polymer product e1:- pressed as` percentagev of ,'mal molecular weighty M'onomer Conversion 60% 60% I 70% l 77% Modiiiers:

CB tert. mercaptans 34.0 52.8 95. 0 100 C12 tert. mercaptans... 34.0 40.6 69.2 100 C14 tert. mercaptans 41.5 50.2 62.5 100 Cs, C12, C14 mercaptan blend l 43.3 63.8 95. 6 100 1 1 partC, Zparts (1312,.2partsA C14 tert. mercaptans.

Fromthe' above table it can be seen that polymers .modified with our mercaptan blend have a higher molecular weight with respect to the iinished product than any of the samples modified with theA individual components of the blend. rIhis effect is even more striking and unexpected when the modifying effect of the individual mer- Captaris is averaged in proportion to the amount of each modifier in the actual blend. Table IV presents a comparison ofthe uniformity of a polymer product actually modified with a blended modifier with a hypothetical case.

TABLE IV Homogeneity of modified GR-S polymers. Calculated versus experimental' values Percentage of Final Molecular Weight Monomer Conversion 50% 60% 70% 77% Hypothetical mercaptan blend 35. 9 47. 0 71. 8 100 Experimental mercaptan blend 43.3 63.8 95.6

7` c catalytic polymerization offreflnery Ca, C4 and C5 olens. These olenic -polymers are fractionated into narrow boiling-rangeicuts"cor-1' responding in 'average molecular weight to octenes, nonenes, decenes, undecenes, dodecenes, etc., prior to conversion to the respective mercaptans. The complexity of isomeric types of the same carbon content inV any one fraction virtually precludes commercial isolation of any one pure mercaptan isomer. However, it is known that mercaptan isomers so produced Vare tertiary in conguration to an extent greater than 95 per cent. While any one of the mer captan groups such as Ca, C12, C14, C16, etc., may be Vused alone as modifiers, the unusual advantages described herein are realized only when blends of two'or vmore groups of isomers are employed. The direct manufacture of our mercaptan blends from olefins of'wide boiling range isV precluded because of `operational and purification diiculties. Y

While considerable attention has been given to the modifying effect of .ternary blends of tertiary mercaptans itis not to be implied that the novel ladvantages .hereinbefore set forth are limited thereto. Inl many instances it may be desirable to employ more' complex blends While in other cases simple Vbinary mixtures may sufce to give the desired modifying eifect. The following examples are appended as illustrating the advantages of our invention with respect to theVV use of blended modifiers comprising binary mixtures of tertiary aliphatic mercaptans.

EXAMPLE I The relative modifying activity of individual tertiary C12 and C14 mercaptans and a blend of these'materials was determined under comparable reaction conditions using equivalent quantities of mercaptan in each instance. The test procedure Wasrras follows: a series of emulsions comprising 75 parts butadiene, 25 parts styrene, 5 parts soap flakes, 0.3 part potassium persulfate and 180 parts water was prepared; modifier was Y added and polymerization effected with constant agitation at 50 C. for variable lengths of timeA in order to follow the progress of modification withA monomer conversion; lthe polymer was recovered andits'intrinsic viscosity was determined. In this manner the eectiveness of tertiary C12 and C14 mercaptans was compared with a 68-32 blend of the respective mercaptans, i. e., 68 partsbyweight of theC12 mercaptan admixed with 32 parts by weight of the C14 mercaptam y The quantities of modifier employed inY these runs were as follows:

Modifier Parts by wt.V

C12 t-II'lercapffm Y 0. 28 C14 t-mercaptan... 0. 40 C12-C14 blelld- 0. 31

'I'he general resultsof these tests and the superi-y orityv'of the blendedv modier is illustrated in Over the; critical .region most. apt tosivecrcss; Y linked and, `inferiorlpolymers itmisinoted that theA curve representing polymer modifiedrvwith the binary blend shows af'higher intrinsic viscosity and therefore 'higher molecular weight fora given 'conversion'than either of the products modified with the Vblend components. This re-V duction in slope of the viscosity-conversion curve with the same ultimate average molecularweight resulted in a more. uniform product'of superior processing and wearing properties.-

HEcxiiMiLEnV Employing the technique of Example I and the same basic recipe, the modifying action of individualV tertiary C12 and Cisl'mercaptans wascompared with a 56-44 blend, respectively, of these mercaptans. The following amounts of modifier;

were `used inthe three series of tests:

` Meer C'mtert'. mercaptans; i' Cw tert. mercaptans C12C1e7blevlld more desirable product was prepared. A curve for polymer modified With C11.` mercaptans could not be constructed since none of the polymer was sufciently modified to be completely soluble in benzene. Thus, in spite of the fact that a relatively large amount of C16 mercaptan modifier was employed, gel formation was pronounced throughout the polymerization period. However, when this C16 tertiary mercaptan is admixed with C12 tertiary mercaptan, a highly satisfactory and superior modifying agent results'.

We claim:

In a process for the production of a modified.

copolymer of butadiene and styrene in an aqueous emulsion, the improvement which comprises the addition asa modifier .of ablend of mixtures of isomeric tertiary aliphaticV mercaptans of uniform molecular weight; said vblend containing substantially the following proportions:A by

weight: one` part of: a( mixture of tertiary octyl. mercaptans, two parts of a mixtur e of tertiary dodecyl mercaptans, and two parts of a mixtureof tertiarytetradecyl mercaptans, to the butadieneV and styrene prior to polymerization.V

` CROUCH'.

' ,'EDWIN G. MARHOFER.`

No references cited.

' rara by wt;

intrinsic visc osity and therefore. 

